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US5661164A - Termite-controlling agent composition - Google Patents

Termite-controlling agent composition Download PDF

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US5661164A
US5661164A US08/532,299 US53229995A US5661164A US 5661164 A US5661164 A US 5661164A US 53229995 A US53229995 A US 53229995A US 5661164 A US5661164 A US 5661164A
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chloro
alkyl
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pyridylmethyl
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US08/532,299
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Yuichi Otsu
Shinzaburo Sone
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Bayer CropScience KK
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Nihon Bayer Agrochem KK
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention relates to a termite-controlling agent.
  • the invention relates to a termite-controlling agent composition showing a synergistic effect, which contains a particular permeable insecticidal compound and a pyrethroid compound.
  • organophosphorus insecticides such as phoxim (chemical name: O-( ⁇ -cyanobenzylideneamino) O,O-diethyl-phosphoro-thioate) and chlorpyrifos (chemical name: O,O-diethyl 3,5,6-trichloro-2-pyridyl-phosphorothioate), and pyrethroid insecticides such as permethrin (chemical name: 5-benzyl-3-furylmethyl-3-(2-methoxy-carbonyl-1-propenyl)-2,2-dimethyl-cyclopropanecarboxylate) and decamethrin (chemical name: ⁇ -cyano-3-pbenoxy-benzyl d,1-cis-3
  • organophosphorus insecticides such as phoxim (chemical name: O-( ⁇ -cyanobenzylideneamino) O,O-diethyl-phosphoro-thioate) and chlorpyrifos (chemical name: O,O
  • the present invention provides termite-controlling agents without such drawbacks; viz. a composition containing effective amounts a compound of the formula ##STR4## wherein, R denotes a hydrogen atom, acyl, alkyl or optionally substituted heteroarylalkyl,
  • A denotes a hydrogen atom, alkyl or a bivalent group which binds to B
  • D denotes alkyl, --S--R 1 , ##STR5## or a bivalent group or atom which binds to A, wherein R 1 and R 2 each independently denotes a hydrogen atom, acyl, alkyl or optionally substituted heteroarylalkyl,
  • T 1 denotes a hydrogen atom or optionally substituted alkyl
  • X denotes an electron attracting group
  • the termite-controlling agent compositions of the invention containing a combination of a compound (a) of the above formula (I) with a pyrethroid compound (b) as an effective ingredient display remarkable synergy and exhibits excellent termite-control at a low concentration which is ineffective for each component us used alone.
  • acyl means, in the broad sense, an acyl group derived from an organic carbonic acid or an organic sulfonic acid, and includes, specifically for example, formyl; alkylcarbonyls such as acetyl and propionyl; arylcarbonyls such as benzoyl; alkylsulfonyls such as methylsulfonyl and ethylsulfonyl, etc.;
  • alkyl can either be straight-chain or branched chain, and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, etc., and preferably lower alkyls having up to 6, particularly up to 4 carbon atom;
  • heteroaryl in the "heteroarylalkyl” is a monocyclic group having at least one hetero atom selected from N, O and S atoms, preferably at least one N atom, and examples of such aromatic heterocyclic groups are thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrazyl, pyridazinyl, etc;
  • the heteroaryl can optionally be substituted; twice or preferably once by, for example, halogen atoms such as fluoro and chloro, alkyl groups such as methyl and ethyl, haloalkyls such as trifluoromethyl and difluoromethyl, alkoxy groups such as methoxy and ethoxy, haloalkoxy groups such as trifluoromethoxy and 2,2,2-trifluoroethoxy, etc.
  • halogen atoms such as fluoro and chloro
  • alkyl groups such as methyl and ethyl
  • haloalkyls such as trifluoromethyl and difluoromethyl
  • alkoxy groups such as methoxy and ethoxy
  • haloalkoxy groups such as trifluoromethoxy and 2,2,2-trifluoroethoxy, etc.
  • bivalent group in the case where the group A denotes "a bivalent group which binds to B" there can be mentioned C 2-4 alkenylene groups such as ethylene, propylene, trimethylene and 1-methyltrimethylene, and the group ##STR7## wherein T denotes a hydrogen atom, an alkyl group or an alkylcarbonyl group.
  • the group B denotes "a bivalent group or atom which binds to A", and thereby the group B combines together with the group A and the carbon atom and nitrogen atom to which these groups bind, to form a nitrogen-containing heterocyclic ring such as, for example, imidazolidine, thiazolidine, tetrahydropyrimidine, piperidine, 2H-1,3-thiazine and hexahydro-1,3,5-triazine.
  • the "bivalent group or atom" which can be denoted by the group B includes methylene, ##STR8## and --S--, etc. wherein T denotes a hydrogen atom, an alkyl group or an alkylcarbonyl group.
  • T 1 includes, for example, halogen such as fluorine, chlorine and bromine; hydroxy; alkoxy such as methoxy and ethoxy; alkylthio such as methylthio and ethylthio; alkenylthio such as allylthio; cyano; mono- or di-alkylamino such as methyl-amino, ethylamino, dimethylamino and diethylamino; alkylcarbonyl, such as acetyl and propionyl; alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl; etc.
  • halogen such as fluorine, chlorine and bromine
  • hydroxy alkoxy such as methoxy and ethoxy
  • alkylthio such as methylthio and ethylthio
  • alkenylthio such as allylthio
  • cyano mono- or di-alkylamino such as methyl-amino,
  • the "electron attracting group" denoted by the group X includes, for example, nitro; cyano; acyl optionally substituted with halogen, such as acetyl, trichloroacetyl and trifluoroacetyl; alkylsulfonyl optionally substituted with halogen, such as methylsulfonyl and trifluoromethylsulfonyl; etc.
  • R denotes a hydrogen atom, formyl, C 1-4 alkylcarbonyl, benzoyl, C 1-4 alkylsulfonyl, C 1-6 alkyl or up to 6-membered heteroarylmethyl which has at least one N atom, can optionally have further hetero atom(s) and can optionally be substituted,
  • A denotes a hydrogen atom, C 1-6 alkyl, ethylene, trimethylene or ##STR9## wherein T 2 denotes a hydrogen atom, C 1-4 alkyl or C 1-4 alkylcarbonyl,
  • D denotes C 1-6 alkyl, --S--R 11 , ##STR10## methylene or ##STR11## wherein R 11 and R 12 each independently denotes a hydrogen atom, formyl, C 1-6 alkylcarbonyl, benzoyl, C 1-4 alkylsulfonyl, C 1-6 alkyl or up to 6-membered heteroarylmethyl which has at least one N atom, can optionally have further hereto atom(s) and can optionally be substituted, and T 3 denotes a hydrogen atom, C 1-4 alkyl or C 1-4 alkylcarbonyl,
  • Y denotes ⁇ N-- or ⁇ CH--
  • X denotes nitro or cyano.
  • R denotes a hydrogen atom, formyl, acetyl, C 1-4 alkyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolyl,
  • A denotes a hydrogen atom, C 1-4 alkyl, ethylene trimethylene or ##STR12## herein T 21 denotes methyl or ethyl, D denotes C 1-4 , alkyl, --S--R 12 , ##STR13## methylene or ##STR14## herein R 12 and R 22 each denote a hydrogen atom, formyl, acetyl, C 1-4 alkyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolyl, and T 31 denotes methyl or ethyl,
  • Y denotes ⁇ N-- or ⁇ CH--
  • X denotes nitro or cyano.
  • Particularly preferred compounds among the compounds of the formula (I) are compounds wherein,
  • R denotes 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolylmethyl
  • A denotes a hydrogen atom, C 1-4 alkyl, ethylene, trimethylene or ##STR15## herein T 21 denotes methyl or ethyl, B denotes C 1-4 alkyl, --S--R 13 , ##STR16## methylene or ##STR17## herein R 13 and R 23 each denote a hydrogen atom, methyl, ethyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolylmethyl, and T 31 denotes methyl or ethyl,
  • Y denotes ⁇ N-- or ⁇ CH--
  • X denotes nitro or cyano.
  • the compounds of the formula (I) are compounds known per se, disclosed in official gazettes such as Japanese Laid-Open Patent Publication Nos. 267575/1986, 171/1990, 235881/1990, 288859/1990 and 154741/1992, and Japanese Patent Publication No. 776/1994, or compound analogous thereto, and can be prepared by the processes described therein or processes analogous thereto.
  • the pyrethroid compounds usable together with the foregoing compounds of the formula (I) according to the invention include all natural and synthetic pyrethroid compounds having a pyrethroid-like insecticidal action, and representative examples thereof are as follows (in the following examples, common names and chemical names are mentioned together).
  • the compounding ratio between the compound (a) of the formula (I) and the pyrethroid compound (b) in the composition of the invention is not strictly limited, and can be varied over a wide range in accordance with the kinds of both ingredients to be combined, etc., but can be in the range of generally 100/1 to 100/100, preferably 100/2 to 100/50 as the weight ratio of the ingredient (a)/the ingredient (b).
  • composition of the invention can further contain, if desired, microbicides (fungicides, bactericides, algaecides) to be used for protecting wood, woody plywood, etc. from damage by microorganisms, etc.
  • microbicides fungicides, bactericides, algaecides
  • Compoundable microbicides include, for example, those mentioned below:
  • Trihalosulfenyl compounds such as, for example,
  • N-(dichlorofluoromethylthio)phthalimide (common name: fluorofolpet).
  • Iodo compounds such as, for example,
  • IPBC 3-iodo-2-propynyl-butyl carbamate
  • Phenolic compounds such as, for example
  • Azole compounds such as, for example,
  • Tin compounds such as, for example,
  • Quaternary ammonium compounds such as, for example,
  • Benzimidazole compounds such as, for example,
  • Isothiazolinone compounds such as, for example,
  • Morpholine compounds such as, for example,
  • N-cyclohexyldiaziniumdioxy compounds such as, for example,
  • Naphthenic acid compounds such as, for example,
  • Nitrile compounds such as, for example,
  • composition of the invention can further contain a synergist, if desired. It is not necessary that the synergist itself is active, and any synergist will do so long as it synergizes at least one of the active ingredients to reinforce the action of the active ingredient.
  • Such a synergist can be compounded in the range of about 0.01 to about 0.3 weight part, preferably about 0.02 to about 0.2 weight part per 1 weight part in total of the compound (a) of the formula (I) and the pyrethroid compound (b).
  • ite-controlling agent composition of the invention when used, can be made into usual formulation forms. These forms include, for example, liquids, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compounds-permeated natural and synthetic materials, microcapsules, etc.
  • formulations can be prepared according to processes known per se.
  • the preparation can be carried out by mixing the active compounds with developers (e.g., liquid diluents, liquefied gas diluents, solid diluents or carriers), and, if desired, surfactants (e.g., emulsifiers, dispersants, foaming agents), etc.
  • developers e.g., liquid diluents, liquefied gas diluents, solid diluents or carriers
  • surfactants e.g., emulsifiers, dispersants, foaming agents
  • organic solvents can, for example, be used as an auxiliary solvent.
  • the liquid diluents or carriers include, for example, aromatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons. (e.g., chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons (e.g., cyclohexane, etc.
  • aromatic hydrocarbons e.g., xylene, toluene, alkylnaphthalene, etc.
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons e.g., chlorobenzenes, ethylene chlorides, methylene chloride, etc.
  • aliphatic hydrocarbons e.g., cyclohexane, etc.
  • paraffins e.g., mineral oil fraction, etc.
  • alcohols e.g., butanol, glycol and their ethers and esters, etc.
  • ketones e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, etc.
  • strongly polar solvents e.g., dimethylformamide, dimethyl sulfoxide, etc.
  • the liquefied gas diluents are those which gasify at ordinary temperature and atmospheric pressure, and examples thereof are aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide and halogenated hydrocarbons.
  • the solid diluents include, for example, soil natural minerals (e.g., kaolin, clay, talc, chalk, attapulgite, montmorillonite, diatom earth, etc.), soil synthetic minerals (e.g., highly dispersed silicic acid, alumina, silicate salts, etc.) etc.
  • soil natural minerals e.g., kaolin, clay, talc, chalk, attapulgite, montmorillonite, diatom earth, etc.
  • soil synthetic minerals e.g., highly dispersed silicic acid, alumina, silicate salts, etc.
  • solid carriers for the granules can be mentioned ground and fractionated stones and rocks (e.g., calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic meals and organic substance powder, fine grains of organic susbstances (e.g, sawdust, the shells of coconuts, the spike axes of corn, stems of tabacco plants, etc.), etc.
  • ground and fractionated stones and rocks e.g., calcite, marble, pumice, sepiolite, dolomite, etc.
  • synthetic granules of inorganic and organic meals and organic substance powder e.g., fine grains of organic susbstances (e.g, sawdust, the shells of coconuts, the spike axes of corn, stems of tabacco plants, etc.), etc.
  • the emulsifiers and/or foaming agents include nonionic and ionic emulsifiers (.e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkyl aryl polyglycol ethers, alkylsulfonate salts, alkyl sulfate salts, arylsulfonate salts, etc.), etc.), albumin hydrolyzates, etc.
  • nonionic and ionic emulsifiers e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkyl aryl polyglycol ethers, alkylsulfonate salts, alkyl sulfate salts, arylsulfonate salts, etc.), etc.
  • albumin hydrolyzates etc.
  • the dispersants include, for example, lignin sulfite waste liquids, methylcellulose, etc.
  • Stickers can also be used in formulations (dusts, granules, emulsions), and include carboxymethylcellulose, natural and synthetic polymers (e.g., gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.), etc.
  • Colorants can also be used, and include inorganic pigments (e.g., iron oxide, titanium oxide and Prussian blue); organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes; microelements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc and their salts; etc.
  • inorganic pigments e.g., iron oxide, titanium oxide and Prussian blue
  • organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes
  • microelements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc and their salts; etc.
  • these formulations can each contain the compound (a) of the formula (I) and the pyrethroid compound (b) in the range of 0.001 to 95% by weight, preferably 0.5 to 90% by weight in total.
  • the weight ratio of (a) to pyrethroid may range from 100:1 to 1:1, advantageously from 50:1 to 5:1, and preferably from 25:1 to 10:1.
  • the composition of the invention has a strong termite-control effect, and can widely be used as a preventive agent or an exterminator on wood, woody plywood, etc. which termites may parasitize in the future or are already parasitizing, or as a treatment agent for soils where termites live or may live in the future.
  • composition of the invention includes:
  • the dosage of the composition of the invention can be varied over a wide range in accordance with the forms of formulation, application places, kinds of termites to be targeted, etc. However generally, the amount can be in the range of about 0.001 g to about 5 g, preferably about 0.002 g to about 3 g, per m 2 as the total amount of the compound of the formula (I) and the pyrethroid compound.
  • compositions of the invention include, for example, painting, application, etc., and the concentrations of the effective ingredients can be in the range of about 0.0001 to about 0.1% by weight, preferably about 0.0002 to about 0.01% by weight as the total amount of the compound of the formula (I) and the pyrethroid compound.
  • Emulsifier polyoxyethylene alkyl phenyl ether 1 weight part
  • Filter paper was placed on glass Petri dishes of diameter 9 cm, and 20 worker-termites and 4 soldier-termites, belonging to Coptotermes formosanus, were put in each Petri dish. 4 ml each of the chemical liquids which had been diluted to the predetermined concentrations according to the above method were applied using microsprayers.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Combating termites with a composition comprising (a) at least one compound of the formula <IMAGE> wherein, R denotes a hydrogen atom, acyl, alkyl or optionally substituted heteroarylalkyl, A denotes a hydrogen atom, alkyl or a bivalent group which binds to B, D denotes alkyl, -S-R1, <IMAGE> or bivalent group or atom which binds to A. wherein R1 or R2 each independently denotes a hydrogen atom, acyl, alkyl or optionally substituted heteroarylalkyl. Y denotes =N- or <IMAGE> wherein T1 denotes a hydrogen atom or optionally substituted alkyl, and X denotes an electron attracting group, and (b) a pyrethoid compound.

Description

The present invention relates to a termite-controlling agent. In more detail, the invention relates to a termite-controlling agent composition showing a synergistic effect, which contains a particular permeable insecticidal compound and a pyrethroid compound.
It is already known, as disclosed, for example, in Japanese Laid-Open Patent Publication Nos. 267575/1986, 235881/1990, 154741/1992, 288859/1990 and 171/1990, Japanese Patent Publication No. 776/1994, that nitromethylene, nitroimino and cyanoimino compounds have excellent insecticidal activity in the field of plant protection. It is further known, as disclosed in Japanese Laid-Open Patent Publication Nos. 56612/1994 and 107510/1994, that these compounds show excellent insecticidal activity as a termite-controlling agent. It is further disclosed in Japanese Laid-Open Patent Publication No. 126805/1988 that a mixed agent of a particular nitroimino compound and a pyrethroid compound has excellent activity as an agrohorticultural insecticide.
On the other hand, chlordane had hitherto been used frequently as a termite-controlling agent in various fields in Japan but its use was prohibited in view of its long-term residual activity and its influence on the environment. Therfore, the chemicals now being used are, mainly, organophosphorus insecticides such as phoxim (chemical name: O-(α-cyanobenzylideneamino) O,O-diethyl-phosphoro-thioate) and chlorpyrifos (chemical name: O,O-diethyl 3,5,6-trichloro-2-pyridyl-phosphorothioate), and pyrethroid insecticides such as permethrin (chemical name: 5-benzyl-3-furylmethyl-3-(2-methoxy-carbonyl-1-propenyl)-2,2-dimethyl-cyclopropanecarboxylate) and decamethrin (chemical name: α-cyano-3-pbenoxy-benzyl d,1-cis-3-(2,2-dibromovinyl)-2,2-dimethyl-cyclopropanecarboxylate).
However these chemicals are not satisfactory because there are limitations on use concentration, the number of times of treatment, safety, effect on wooden houses (residences), and the like, etc.
The present invention provides termite-controlling agents without such drawbacks; viz. a composition containing effective amounts a compound of the formula ##STR4## wherein, R denotes a hydrogen atom, acyl, alkyl or optionally substituted heteroarylalkyl,
A denotes a hydrogen atom, alkyl or a bivalent group which binds to B,
D denotes alkyl, --S--R1, ##STR5## or a bivalent group or atom which binds to A, wherein R1 and R2 each independently denotes a hydrogen atom, acyl, alkyl or optionally substituted heteroarylalkyl,
Y denotes ═N-- or ##STR6## Wherein T1 denotes a hydrogen atom or optionally substituted alkyl, and
X denotes an electron attracting group,
and
(b) a pyrethroid compound.
Surprisingly, the termite-controlling agent compositions of the invention containing a combination of a compound (a) of the above formula (I) with a pyrethroid compound (b) as an effective ingredient display remarkable synergy and exhibits excellent termite-control at a low concentration which is ineffective for each component us used alone.
In the compounds of the above formula (I) used as an effective ingredient in the composition of the invention,
the term "acyl" means, in the broad sense, an acyl group derived from an organic carbonic acid or an organic sulfonic acid, and includes, specifically for example, formyl; alkylcarbonyls such as acetyl and propionyl; arylcarbonyls such as benzoyl; alkylsulfonyls such as methylsulfonyl and ethylsulfonyl, etc.;
"alkyl" can either be straight-chain or branched chain, and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, etc., and preferably lower alkyls having up to 6, particularly up to 4 carbon atom;
the heteroaryl in the "heteroarylalkyl" is a monocyclic group having at least one hetero atom selected from N, O and S atoms, preferably at least one N atom, and examples of such aromatic heterocyclic groups are thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrazyl, pyridazinyl, etc;
the heteroaryl can optionally be substituted; twice or preferably once by, for example, halogen atoms such as fluoro and chloro, alkyl groups such as methyl and ethyl, haloalkyls such as trifluoromethyl and difluoromethyl, alkoxy groups such as methoxy and ethoxy, haloalkoxy groups such as trifluoromethoxy and 2,2,2-trifluoroethoxy, etc.
As the "bivalent group" in the case where the group A denotes "a bivalent group which binds to B" there can be mentioned C2-4 alkenylene groups such as ethylene, propylene, trimethylene and 1-methyltrimethylene, and the group ##STR7## wherein T denotes a hydrogen atom, an alkyl group or an alkylcarbonyl group.
On the other hand, in the case where the group A denotes the above bivalent group, the group B denotes "a bivalent group or atom which binds to A", and thereby the group B combines together with the group A and the carbon atom and nitrogen atom to which these groups bind, to form a nitrogen-containing heterocyclic ring such as, for example, imidazolidine, thiazolidine, tetrahydropyrimidine, piperidine, 2H-1,3-thiazine and hexahydro-1,3,5-triazine. Thus, the "bivalent group or atom" which can be denoted by the group B includes methylene, ##STR8## and --S--, etc. wherein T denotes a hydrogen atom, an alkyl group or an alkylcarbonyl group.
The possible substituent in "optionally substituted alkyl" which can be denote by T1 includes, for example, halogen such as fluorine, chlorine and bromine; hydroxy; alkoxy such as methoxy and ethoxy; alkylthio such as methylthio and ethylthio; alkenylthio such as allylthio; cyano; mono- or di-alkylamino such as methyl-amino, ethylamino, dimethylamino and diethylamino; alkylcarbonyl, such as acetyl and propionyl; alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl; etc.
The "electron attracting group" denoted by the group X includes, for example, nitro; cyano; acyl optionally substituted with halogen, such as acetyl, trichloroacetyl and trifluoroacetyl; alkylsulfonyl optionally substituted with halogen, such as methylsulfonyl and trifluoromethylsulfonyl; etc.
Thus, preferred compounds among the compounds of the above formula (I) are compounds wherein,
R denotes a hydrogen atom, formyl, C1-4 alkylcarbonyl, benzoyl, C1-4 alkylsulfonyl, C1-6 alkyl or up to 6-membered heteroarylmethyl which has at least one N atom, can optionally have further hetero atom(s) and can optionally be substituted,
A denotes a hydrogen atom, C1-6 alkyl, ethylene, trimethylene or ##STR9## wherein T2 denotes a hydrogen atom, C1-4 alkyl or C1-4 alkylcarbonyl,
D denotes C1-6 alkyl, --S--R11, ##STR10## methylene or ##STR11## wherein R11 and R12 each independently denotes a hydrogen atom, formyl, C1-6 alkylcarbonyl, benzoyl, C1-4 alkylsulfonyl, C1-6 alkyl or up to 6-membered heteroarylmethyl which has at least one N atom, can optionally have further hereto atom(s) and can optionally be substituted, and T3 denotes a hydrogen atom, C1-4 alkyl or C1-4 alkylcarbonyl,
Y denotes ═N-- or ═CH--, and
X denotes nitro or cyano.
Further preferred compounds among the compounds of the formula (I) are compounds wherein,
R denotes a hydrogen atom, formyl, acetyl, C1-4 alkyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolyl,
A denotes a hydrogen atom, C1-4 alkyl, ethylene trimethylene or ##STR12## herein T21 denotes methyl or ethyl, D denotes C1-4, alkyl, --S--R12, ##STR13## methylene or ##STR14## herein R12 and R22 each denote a hydrogen atom, formyl, acetyl, C1-4 alkyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolyl, and T31 denotes methyl or ethyl,
Y denotes ═N-- or ═CH--, and
X denotes nitro or cyano.
Particularly preferred compounds among the compounds of the formula (I) are compounds wherein,
R denotes 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolylmethyl,
A denotes a hydrogen atom, C1-4 alkyl, ethylene, trimethylene or ##STR15## herein T21 denotes methyl or ethyl, B denotes C1-4 alkyl, --S--R13, ##STR16## methylene or ##STR17## herein R13 and R23 each denote a hydrogen atom, methyl, ethyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolylmethyl, and T31 denotes methyl or ethyl,
Y denotes ═N-- or ═CH--, and
X denotes nitro or cyano.
Preferred specific examples of the compounds of the formula (I) used as one of the effective ingredients in the invention are as follows.
1-(6-chloro-3-pyridylmethyl)-N-nitro-imidazolidin-2-ylideneamine,
N-cyano-N-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine,
1-[N-(6-chloro-3-pyridylmethyl)-N-ethylamino]-1-methylamino-2-nitro-ethylene,
1-(2-chloro-5-pyridylmethyl)-5-methyl-2-nitroimino-hexahydro-1,3,5-triazine
1-(2-chloro-5-thiazolylmethyl)-3,5-dimethyl-2-nitroimino-hexahydro-1,3,5-triazine,
1-(2-chloro-5-pyridylmethyl)-3,5-dimethyl-2-nitroimino-hexahydro-1,3,5-triazine,
1-(2-chloro-5-pyridylmethyl)-2-nitromethylene-imidazolidine,
1-[N-(2-chloro-5-thiazolylmethyl)-N-ethylamino]-1-methylamino-2-nitro-ethylene,
3-(2-chloro-5-pyridylmethyl)-2-nitromethylene-thiazolidine,
1-(2-chloro-5-pyridylmethyl)-2-(1-nitro-2-allylthioethylidene)imidazolidine
1-(2-chloro-5-pyridylmethyl)-2-(1-nitro-2-ethylthioethylidene)imidazolidine
1-(2-chloro-5-pyridylmethyl)-2-(1-nitro-2-β-methyl-allylthioethylidene)imidazolidine,
methyl [3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitro]guanidinoformate,
1-(2-chloro-5-pyridylmethylamino)-1-methylthio-2-nitroethylene,
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene,
1-(2-chloro-5-pyridylmethyl)-3-nitro-2-methylisothiourea,
3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitroguanidine,
1-(2-chloro-5-pyridylmethylamino)-1-dimethylamino-2-nitroethylene,
1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-1-methylamino-2-nitro-ethylene,
1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-1-dimethylamino-2-nitro-ethylene,
3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine,
1-(2-chloro-5-pyridylmethylamino)-1-ethylamino-2-nitroethylene,
1-amino-1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-2-nitroethylene,
3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine,
3-(2-chloro-5-pyridylmethyl)-1,1,3-trimethyl-2-nitroguanidine,
1-amino-1-[N-(2-chloro-5-pyridylmethyl)-N-ethylamino]-2-nitroethylene,
1-[N-(2-chloro-5-pyridylmethyl)-N-n-propylamino]-1-methylamino-2-nitro-ethylene,
3-(2-chloro-5-thiazolylmethyl)-1-methyl-2-nitroguanidine,
1-[N-(2-chloro-5-pyridylmethyl)-N-ethylamino]-1-ethylamino-2-nitro-ethylene, and
3-(2-chloro-5-pyridylmethyl)-3-ethyl-1-methyl-2-nitroguanidine, etc.
The compounds of the formula (I) are compounds known per se, disclosed in official gazettes such as Japanese Laid-Open Patent Publication Nos. 267575/1986, 171/1990, 235881/1990, 288859/1990 and 154741/1992, and Japanese Patent Publication No. 776/1994, or compound analogous thereto, and can be prepared by the processes described therein or processes analogous thereto.
On the other hand, the pyrethroid compounds usable together with the foregoing compounds of the formula (I) according to the invention include all natural and synthetic pyrethroid compounds having a pyrethroid-like insecticidal action, and representative examples thereof are as follows (in the following examples, common names and chemical names are mentioned together).
______________________________________                                    
Common name                                                               
          Chemical name                                                   
______________________________________                                    
allethrin:                                                                
          (±)-3-allyl-2-methyl-4-oxocyclopent-2-enyl                   
          (±)cis-trans-chrysanthemate,                                 
cyfluthrin:                                                               
          (RS)-α-cyano-4-fluoro-3-phenoxybenzyl                     
          (1RS,3RS)-(1RS,3SR)-3-(2,2-dichlorvinyl)-2,2-                   
          dimethylcyclopropanecarboxylate,                                
cypermethrin:                                                             
          (RS)-α-cyano-3-phenoxybenzyl(1RS,3RS)-                    
          (1RS,3SR)-chrysanthemate,                                       
decamethrin:                                                              
          (S)-α-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-                
          dibromovinyl)-2,2-dimethylcyclopropane-                         
          carboxylate,                                                    
fenpropathrin:                                                            
          (RS)-α-cyano-3-phenoxybenzyl-2,2,3,3-tetra-               
          methyl-cyclopropanecarboxylate,                                 
permethrin:                                                               
          3-phenoxybenzyl(1RS,3RS)-(1RS,3SR)-3-                           
          (2,2-dichlorovinyl)-2,2-                                        
          dimethylcyclopropanecarboxylate,                                
rethmethrin:                                                              
          5-benzyl-3-furylmethyl(±)-cis-trans-                         
          chrysanthemate,                                                 
fluvalinate:                                                              
          (RS)-α-cyano-3-phenoxybenzyl N-(2-chloro-                 
          α,α,α-trifluoro-p-toluyl)-D,L-valinate,       
tralomethrin:                                                             
          (S)-α-cyano-3-phenoxybenzyl(1R)-cis-2,2-                  
          dimethyl-3-[(RS)-1,2,2,2-tetrabromoethyl]-                      
          cyclopropanecarboxylate,                                        
fenvalerate:                                                              
          (RS)-α-cyano-3-phenoxybenzyl-(RS)-2-(4-                   
          chlorophenyl)-3-methylbutyrate,                                 
silafluofen:                                                              
          (4-ethoxyphenyl)[3-(4-fluoro-3-phenoxy-phenyl)                  
          propyl]dimethylsilane,                                          
teflutrin:                                                                
          2,3,5,6-tetrafluoro-4-methylbenzyl(2)-(1RS,3RS)-                
          3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-                    
          dimethylcyclopropanecarboxylate,                                
ethofenprox:                                                              
          2-(4-ethoxyphenyl)-2-methylpropyl                               
          3-phenoxybenzyl ether,                                          
and                                                                       
bifenthrin:                                                               
          3-phenoxybenzyl(1R,3R)-3-(2,2-dichlorovinyl)-2,                 
          2-dimethyl-cyclopropanecarboxylate, e.t.c.                      
______________________________________
The compounding ratio between the compound (a) of the formula (I) and the pyrethroid compound (b) in the composition of the invention is not strictly limited, and can be varied over a wide range in accordance with the kinds of both ingredients to be combined, etc., but can be in the range of generally 100/1 to 100/100, preferably 100/2 to 100/50 as the weight ratio of the ingredient (a)/the ingredient (b).
The composition of the invention can further contain, if desired, microbicides (fungicides, bactericides, algaecides) to be used for protecting wood, woody plywood, etc. from damage by microorganisms, etc.
Compoundable microbicides (fungicides, bactericides and algaecides) include, for example, those mentioned below:
Trihalosulfenyl compounds such as, for example,
N-(dichlorofluoromethylthio)-N,N'-dimethyl-N-phenylsulfamide (common name: dichlofluanide),
N-(dichlorofluoromethylthio)-N',N'-dimethyl-N-P-tolylsulfamide (common name: tolylfluanide),
N-(trichloromethylthio)phthalimide (common name: folpet),
N-(dichlorofluoromethylthio)phthalimide (common name: fluorofolpet).
Iodo compounds such as, for example,
3-iodo-2-propynyl-butyl carbamate (IPBC),
3-iodo-2-propynyl-hexyl carbamate,
3-iodo-2-propynyl-cyclohexyl carbamate,
3-iodo-2-propynyl-phenyl carbamate,
diiodomethyl-p-tolylsulfone (common name: amical 48) and
3-bromo-2,3-diiodo-2-propenyl ethyl carbonate.
Phenolic compounds such as, for example
o-phenylphenol,
tribromophenol,
tetrachlorophenyl and
pentachlorophenol.
Azole compounds such as, for example,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone (common name: triadimefon),
β-(4-chlorophenoxy)-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (common name: triadimenol),
±α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (common name: tebuconazol),
1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole (common name: propiconazol),
1-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole (common name: azaconazol), and
1-{N-propyl-N-[2-(2,4,6-(trichlorophenoxy)ethyl]carbamoyl}imidazole (common name: prochloraz).
Tin compounds such as, for example,
methylene bisthiocyanate (MBT) and
2-thiocyanomethylthiobenzothiazole (TCMTB).
Quaternary ammonium compounds such as, for example,
benzyl-dimethyl-tetradecylammonium chloride and
benzyl-dimethyl-dodecylammonium chloride.
Benzimidazole compounds such as, for example,
2-(2'-furyl)-1H-benzimidazole (common name: fuberidazole),
methyl benzimidazol-2-ylcarbamte (BCM),
2-(4'-thiazolyl)benzimidazole (common name: thiabendazole) and
methyl (1-butylcarbamoyl)-2-benzimidazolecarbamate (common name: benomyl).
Isothiazolinone compounds such as, for example,
N-methylisothiazolin-3-one.
5-chloro-N-methylisothiazolin-3-one,
4,5-dichloro-N-octylisothiazolin-3-one and
N-octylisothiazolin-3-one.
Morpholine compounds such as, for example,
C14 -C11 -4-alkyl-2,6-dimethylmorpholine (common name: tridemorph).
Pyridine compounds such as, for example,
1-hydroxy-2-pyridine-thione and its sodium iron salt, manganese salt and zinc salt
tetrachloro-4-methylsulfonylpyridine.
N-cyclohexyldiaziniumdioxy compounds such as, for example,
tris-(N-cyclohexyldiaziniumdioxy)aluminum and
bis-(N-cyclohexyldiaziniumdioxy)copper.
Naphthenic acid compounds such as, for example,
zinc naphthenate.
Quinoline compounds such as, for example,
8-hydroxyquinoline copper salt.
and
Nitrile compounds such as, for example,
1,2,3,5-tetrachloro-4,6-cyanobenzene.
The composition of the invention can further contain a synergist, if desired. It is not necessary that the synergist itself is active, and any synergist will do so long as it synergizes at least one of the active ingredients to reinforce the action of the active ingredient.
Examples of these synergists are as follows.
______________________________________                                    
Common name Chemical name                                                 
______________________________________                                    
Sesamex:    4-[1-[2-(2-ethoxyethoxy)ethoxy]ethoxy]-1,2-                   
            methylene-dioxybenzene,                                       
Sulfoxide:  2-(1,3-benzodioxy-5-yl)=ethyloctyl                            
            sulfoxide,                                                    
Piprotal:   5-[bis[2-[(2-butoxyethoxy)=ethoxy]methyl]-                    
            1,3-benzodioxole,                                             
Sesasmolin: 1,3-benzodioxol-5-yl(1R,3aR,4S,6aR)-4-(1,3-                   
            benzodioxol-5-yl)perhydrofuro[3,4-c]                          
            furan-1-yl ether,                                             
Sesamine:   1,4-di-(1,3-benzodioxol-5-yl)tetrahydrofuro                   
            [3,4-c]furan,                                                 
Safroxan:   4-(3,4-methylenedioxyphenyl-5-methyl-m-                       
            dioxane                                                       
Safroxane:  4-(3,4-methylenedioxy-6-propylphenyl)-                        
            5-methyl-1,3-dioxane,                                         
piperonyl butoxide,                                                       
octachlorodipropyl                                                        
ether, etc.                                                               
______________________________________
Such a synergist can be compounded in the range of about 0.01 to about 0.3 weight part, preferably about 0.02 to about 0.2 weight part per 1 weight part in total of the compound (a) of the formula (I) and the pyrethroid compound (b).
The termite-controlling agent composition of the invention, when used, can be made into usual formulation forms. These forms include, for example, liquids, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compounds-permeated natural and synthetic materials, microcapsules, etc.
These formulations can be prepared according to processes known per se. For example, the preparation can be carried out by mixing the active compounds with developers (e.g., liquid diluents, liquefied gas diluents, solid diluents or carriers), and, if desired, surfactants (e.g., emulsifiers, dispersants, foaming agents), etc. When water is used as the developer, organic solvents can, for example, be used as an auxiliary solvent.
The liquid diluents or carriers include, for example, aromatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons. (e.g., chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons (e.g., cyclohexane, etc. and paraffins (e.g., mineral oil fraction, etc.)), alcohols (e.g., butanol, glycol and their ethers and esters, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, etc.), strongly polar solvents (e.g., dimethylformamide, dimethyl sulfoxide, etc.), water, etc.
The liquefied gas diluents are those which gasify at ordinary temperature and atmospheric pressure, and examples thereof are aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide and halogenated hydrocarbons.
The solid diluents include, for example, soil natural minerals (e.g., kaolin, clay, talc, chalk, attapulgite, montmorillonite, diatom earth, etc.), soil synthetic minerals (e.g., highly dispersed silicic acid, alumina, silicate salts, etc.) etc.
As solid carriers for the granules can be mentioned ground and fractionated stones and rocks (e.g., calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic meals and organic substance powder, fine grains of organic susbstances (e.g, sawdust, the shells of coconuts, the spike axes of corn, stems of tabacco plants, etc.), etc.
The emulsifiers and/or foaming agents include nonionic and ionic emulsifiers (.e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkyl aryl polyglycol ethers, alkylsulfonate salts, alkyl sulfate salts, arylsulfonate salts, etc.), etc.), albumin hydrolyzates, etc.
The dispersants include, for example, lignin sulfite waste liquids, methylcellulose, etc.
Stickers can also be used in formulations (dusts, granules, emulsions), and include carboxymethylcellulose, natural and synthetic polymers (e.g., gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.), etc.
Colorants can also be used, and include inorganic pigments (e.g., iron oxide, titanium oxide and Prussian blue); organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes; microelements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc and their salts; etc.
Generally, these formulations can each contain the compound (a) of the formula (I) and the pyrethroid compound (b) in the range of 0.001 to 95% by weight, preferably 0.5 to 90% by weight in total. The weight ratio of (a) to pyrethroid may range from 100:1 to 1:1, advantageously from 50:1 to 5:1, and preferably from 25:1 to 10:1.
As apparent from the later-described test example, the composition of the invention has a strong termite-control effect, and can widely be used as a preventive agent or an exterminator on wood, woody plywood, etc. which termites may parasitize in the future or are already parasitizing, or as a treatment agent for soils where termites live or may live in the future.
Examples of termites controllable by the composition of the invention includes:
Deucotermes speratus, Coptotermes formosanus, Glyptotermes fucus, Glyptotermes satsumensis, Glyptotermes nakajimai, Glyptotermes kodamai, Incisitermes minor, Neotermes koshunensis, Glyptotermes domesticus, Hodotermopsis japonica, Reticulitermes miyatakei, Odontotermes formosauns, Nlasutitermes takasagoensis, Capritermes nitobei, etc.
The dosage of the composition of the invention can be varied over a wide range in accordance with the forms of formulation, application places, kinds of termites to be targeted, etc. However generally, the amount can be in the range of about 0.001 g to about 5 g, preferably about 0.002 g to about 3 g, per m2 as the total amount of the compound of the formula (I) and the pyrethroid compound.
Application methods for the composition of the invention include, for example, painting, application, etc., and the concentrations of the effective ingredients can be in the range of about 0.0001 to about 0.1% by weight, preferably about 0.0002 to about 0.01% by weight as the total amount of the compound of the formula (I) and the pyrethroid compound.
This invention is further specifically described in the following illustrative examples.
EXAMPLE 1 Termite-Control Test
A. Test Compounds
(a) Compounds of the formula (I)
(a)-1: 1-(6-chloro-3-pyridylmethyl)-2-nitro-imidazolidin-2-ylideneamine
(a)-2: N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine
(b) Pyrethroid compounds
(b)-1: cyfluthrin (common name)
(b)-2: permethrin (common name)
(c) Synergist
(c)-1: piperonyl butoxide
B. Preparation of Test Chemical Liquids
Solvent: xylol 3 weight parts
Emulsifier: polyoxyethylene alkyl phenyl ether 1 weight part
In order to prepare a suitable formulation, 1 weight part in total of the compound of the formula (I), the pyrethroid compound and the synergist was mixed with the above-mentioned amount of the solvent containing the above-mentioned amount of the emulsifer, and the mixture was diluted with water to a predetermined concentration to give a test chemical liquid.
C. Test Method
Filter paper was placed on glass Petri dishes of diameter 9 cm, and 20 worker-termites and 4 soldier-termites, belonging to Coptotermes formosanus, were put in each Petri dish. 4 ml each of the chemical liquids which had been diluted to the predetermined concentrations according to the above method were applied using microsprayers.
The Petri dishes were moved to a constant temperature room of 25° C.; 24 hours after the chemical treatment, the number of dead worker-termites were counted; and the mortality was calculated. This test was carried out in two replicates. The results are shown in the following Table 1.
              TABLE 1                                                     
______________________________________                                    
                 Concentrations of                                        
                              Insecticidal                                
Active compound  effective    rate after 24                               
- Synergist      ingredients (ppm)                                        
                              hours (%)                                   
______________________________________                                    
(a) - 1 + (b) - 1                                                         
                 40 + 1.6     95                                          
                 40 + 0.8     93                                          
                 8 + 1.6      90                                          
                 8 + 0.8      78                                          
(a) - 1 + (b) - 1 + (c) - 1                                               
                 8 + 0.8 + 1.6                                            
                              95                                          
(a) - 2 + (b) - 1                                                         
                 8 + 1.6      100                                         
                 8 + 0.8      95                                          
                 1.6 + 1.6    90                                          
                 1.6 + 0.8    88                                          
(a) - 1 + (b) - 2                                                         
                 40 + 1.6     95                                          
                 40 + 0.8     95                                          
                 8 + 1.6      90                                          
                 8 + 0.8      88                                          
(a) - 1          40           65                                          
                 8            8                                           
(a) - 2          8            78                                          
                 1.6          60                                          
(b) - 1          1.6          33                                          
                 0.8          20                                          
(b) - 2          1.6          25                                          
                 0.8          20                                          
(c) - 1          1.6          0                                           
Untreated        --           0                                           
______________________________________
The following examples illustrate suitable formulations:
EXAMPLE 2 Oil Solution 
______________________________________                                    
                     wt %                                                 
______________________________________                                    
Active Compound (a)-   10.004                                             
(described in Ex. 1)                                                      
Cyfluthrin (common name)                                                  
                       0.00016                                            
Tebuconazol (common name)                                                 
                       1.2                                                
Dipropylene glycol monomethyl ether                                       
                       10.0                                               
Odorless kerosene      88.79584                                           
______________________________________
The above components are mixed to give an oil solution.
EXAMPLE 3 Emulsion 
______________________________________                                    
                      wt %                                                
______________________________________                                    
Active Compound (a)-1   0.1                                               
(described in Ex. 1)                                                      
Cyfluthrin (common name)                                                  
                        0.004                                             
Polyoxyethylene tristyryl phenyl ether                                    
                        4.0                                               
Calcium dodecylbenzenesulfonate                                           
                        1.0                                               
Xylene                  94.896                                            
______________________________________
The above components are mixed by stirring to give an emulsion.
It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.

Claims (4)

We claim:
1. A method of combatting termites which comprises applying to said termites or to an infested habitat habitat to which they reside a synergistic termite-controlling composition which comprises synergistic effective amounts of
a) 1-(6-chloro-3-pyridylmethyl)-2-nitro-imidazolidin-2-ylideneamine; and
b) cyfluthrin
wherein the weight ratio of component a to component b is from 50:1 to 5:1 and an inert carrier.
2. The method according to claim 1, wherein the weight ratio of component a to component b is from 25:1 to 10:1.
3. The method according to claim 1, wherein the weight ratio of component a to component b is 25:1.
4. The method according to claim 1, wherein the weight ratio of component a to component b is 5:1.
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